Mass Transfer

(CLPC18)

[Link]. (Chemical Engineering)

IV Semester
January 2021 Session
 Text Books
1. R. E. Treybal, "Mass Transfer Operations", 3rd Edn., McGraw Hill Book Co., New
York, 1981.
2. N. Anantharaman and [Link] Sheriffa Begum, “Mass Transfer Theory and
Practice”, Printice Hall of India Pvt. Ltd., New Delhi, 2013.
3. K.V. Narayanan and [Link], “Mass Transfer: Theory and Applications”, 1st
Edition, CBS Publishers & Distributors Pvt Ltd., New Delhi, 2014
4. [Link], “Principles of Unit Operations”, 2nd Edition, Wiley & Sons, New York, 1980.
5. J. M. Coulson and J. F. Richardson, "Chemical Engineering", 5th Edition Vol. II, P Butterworth
Heinemann, New, 2002.
6. [Link], “Transport Processes and Separation Process Principles,” IV edition, Prentice Hall of
India Pvt. Ltd, New Delhi, 2004.
7. W.L. McCabe, J.C. Smith and P. Harriot, "Unit Operations of Chemical Engineering", 7th Edn., McGraw
Hill Book Co., New York, 2004.
Importance of Mass Transfer

 Chemical Process Industries: Raw materials into useful products

 Examples: petroleum products & petrochemicals, inorganic & organic chemicals,
paints & pigments, fertilizers & pesticides, pulp & paper, rubber & plastics, soaps &
detergents, pharmaceuticals, metals, etc.

 Uses of Products:
 Day to day life, raw materials, intermediates

 Products undergo processing steps:

 Physical or chemical process to achieve desired quality & specifications
 Raw materials pre-processing
 Treating products contaminated with by products
 Removing unconverted reactants and impurities

Pre-processing/ Recovery/ purification involves separation operations

Separation Operations

 Objectives of Separation Operations

 Purification, isolation, recovery, refining, concentration, enrichment of the materials

 How to achieve Separation?

 Differences in their properties

 Size, density, volatility, solubility, diffusivity, electrical charge,…..

 Categories of separation operation

 Mechanical Separations
 Diffusional Separations

 Mechanical Separations
 Examples: Filtration, screening, sedimentation, magnetic separation, centrifuging, etc
 Properties: size, density, velocity, etc.
 Diffusional Separations
Diffusional Separations known as Mass Transfer Operations

 Separating components of a homogeneous solution

 Properties: volatility, solubility, diffusivity,…

Movement of material:
Concentration difference
From higher concentration to lower concentration

Diffusion
Basic mechanism of Mass Transfer
 Equilibrium in Mass Transfer

Thermodynamics
 When different phases coexist in equilibrium then the chemical
potentials of the components in the different phases should be equal
 Concentrations of the components in the phases need not be equal at
equilibrium
 Concentration difference is just measure of the driving force for Mass
Transfer but not the true driving force
 True Driving Force

Difference in the Chemical Potential of the species in the different phases

 Different Contact Operations

Gas – Liquid contact operations:

• Gas Absorption & Desorption
• Distillation
• Humidification & Dehumidification
Liquid – Liquid contact operations:
• Extraction
Solid – Liquid/Gas contact operations:
• Leaching
• Drying
• Adsorption
• Crystallization
 Different Contact Operations

Membrane Separation Operations:

• Unconventional separation technique
• Highly suited for heat sensitive materials

• High selectivity & permeability, compact, less energy intensive

Organic & Inorganic membranes

• Materials: Natural polymers, Synthetic polymers, ceramic, metal, carbon,
zeolite membranes
 Molecular Diffusion

Molecular Diffusion Primary Mechanism

Molecular Diffusion Slow process

Most of the mass transfer operations involve transfer of materials

between phases

Molecular Diffusion between phases

 From one phase to the interface
 From the interface to the other phase
Basic Definitions of Diffusion Process
Concentrations
 Mass Concentration (ρ)
The mass of the component in one cubic meter of the solution
n
   i
 Molar Concentration (C) 1

The number of moles of component

n
per unit volume of the solution
C   Ci
i
 Molar and Mass Concentration relation Ci 
1

Mi
i
 Mass fraction i    Mole fraction xi 
Ci
C
 Sum of all mole
n
fractions (or mass fractions) in a mixture is unity
x
n

1
i 1 
1
i 1

 For gases C  ni  pi C   C   pi P
n n
i V 
RT 1
i
1 RT RT
Basic Definitions of Diffusion Process
Velocity
 Mass Average Velocity (u)
Mass fraction weighted average of the velocities of the components
n
constituting the mixture

u  i ui
1
 Molar Average Velocity (U)
Mole fraction weighted average nof the velocities of the components
constituting the mixture U   xi ui
1

 Diffusion velocity of species i relative to the mass average velocity of the

ui  ui  u
mixture

 Diffusion velocity of species i relative to the molar average velocity of the

mixture
U i  ui  U
Basic Definitions of Diffusion Process
Flux
The rate at which a material is transferred by molecular diffusion is directly
proportional to the area normal to the direction of transfer.
 Definition of Flux
The rate of mass or molar units that pass a unit area normal to the direction of
transfer in unit time.
Flux = Concentration × Velocity
Kg/m2h or kmol/m2h

Molar average velocity of the fluid (JA)

Flux
Stationary coordinate axis (NA)
Basic Definitions of Diffusion Process
Flux
The rate of transfer of species is the sum of two contributions:
 Molecular diffusion Concentration difference
 Bulk flow contribution Transfer by convective transport

N A  C Au A J A  C AU A
N A  J A  xA N
N = Total rate of transfer of the fluid by bulk flow

N = NA + NB
Basic Definitions of Diffusion Process
Fick’s Law of Diffusion
The following generalization are made regarding molecular diffusion
 The rate of molecular diffusion is directly proportional to the surface normal
to the direction of transfer.
 The rate can be expressed as a flux for the component diffusing.
 Diffusion occurs in the direction of decreasing concentration & is
proportional to the negative concentration gradient.
dC A
J A   DAB Kmol/m2h or kmol/m2s
dz
dx A
J A  CDAB
dz
 dC A
Fick’s Law of Diffusion J A   DAB
dz
DAB – Binary mass diffusivity
 Characteristic of the substance A and B of the mixture.
 Strongly influenced by physical state such as Temperature, Pressure & Concentration

-14 -10 2
Solids : 10 to 10 m /s
-10 -9 2
Liquids : 10 to 10 m /s
Gases : 5 10 to 10 m /s
-6 -5 2
Generalized flux equation
J A  C AU A  C A  u A  U  U  xAu A  xBuB
CA CB
C Au A  J A  C AU U
C
uA 
C
uB
CA
C Au A  J A 
C
CAu A CBu B 

NA NA NB
NA + NB N

N A  J A  xA N N A   DAB dC A
 xA N
dz

N A  CDAB dxA  xA N
dz
 Relationship between DAB and DBA
N = NA + NB N   DAB dC A  xA N  DBA dCB  xB N
dz dz

N   DAB dC A
 DBA
dCB
  x A  xB  N
dz dz
1
N   DAB dC A
 DBA
dCB
N
dz dz
dC A dCB dC A dCB
 DAB  DBA 0  DAB  DBA
dz dz dz dz
dxA dxB
 DAB  DBA J A  J B
dz dz
dxA dxB
DAB  DBA 
dz dz
Steady State Molecular Diffusion in Gases
Two cases of steady state diffusion
 Equimolar Counter Diffusion
 Diffusion through stagnant gases
Equimolar Counter Diffusion
 The number of moles of A moving in one direction is equal to the number of moles
of B moving in the opposite direction
 Net molar flow in either direction or the net motion of the entire phase is zero
N = NA + NB N = NA + NB = 0 NA = - NB
dC A  CD dy A
N A  J A  xA N NA  JA   DAB AB dz
dz

N A dz  CDAB dy A
z2 yA 2

N A dz    CDAB dy A N A Z  CDAB  y A2  y A1 
z1 y A1

N A Z  CDAB  y A1  y A2  NA 
CDAB
 y A1  y A2  NA 
DAB
 pA1  pA2 
Z RTZ
 Diffusion through stagnant gases
 One component will be transported & the other will undergo no net movement.
N = NA + NB N = NA NB = 0

N A  J A  yA N A N A  CDAB dy A  y A N A N A 1  y A   CDAB dy A
dz dz
z2 yA 2
CDAB
N Adz   dy A N A  dz  CDAB  dy A
NA 
CDAB 1  y A2
 A
1  y
z1 y A1 
1  yA  Z
ln
1  y A1

CDAB CDAB yB 2
NA   y A1  y A2  NA  ln
ZyBM Z yB1

yB 2  yB1 y A1  y A 2
yBM   Logarithmic Mean of yB2 & yB1
ln( yB 2 / yB1 ) ln( yB 2 / yB1 )

DAB P pB 2 DAB P
NA  ln NA   pA1  pA2 
RTZ pB1 RTZ pBM
 Generalized Equation for Steady-State Diffusion
N A  J A  yA N A N A   DAB dC A  y A  N A  N B  N A   DAB dC A  C A  N A  N B 
dz dz C
z2 CA 2
  dz   
dC A
CN A  CA  N A  N B   CDAB dC A
dz dC A 1
dz CDAB CN A  CA  N A  N B  CDAB z 1 C A1 CN A  CA  N A  N B 

CN A  CA2  N A  N B  CN A  CA2  N A  N B 
Z
 1
ln NA 
CDAB NA
ln
CDAB N A  N B CN A  CA1  N A  N B  Z N A  N B CN A  CA1  N A  N B 

NA CA 2 NA
  y A2
NA 
CDAB NA  N A  NB  C  N A  NB 
NA 
ln CDAB NA
ln
Z N A  NB NA C Z N A  NB NA
 A1  y A1
 N A  NB  C  N A  NB 

N A = - NB NB = 0
 Diffusion in Multicomponent Mixtures
n

CDA,m 1  y A2 N A  y A  Ni
NA  ln DA , m  i A
DA , m 
1  yA

1
Z 1  y A1 n
yi N A  y A N i

n n
yi
DAi 
i  B DAi

yi
i A i  B DAi

Prediction of Binary Diffusivities

Diffusivity of Gases
 Semi-theoretical correlations using Kinetic Theory of Gases
Hirschfelder-Bird-Spotz Equation
2.6628 104 T 3/2 Where, T & P are absolute temperature and pressure
DAB  σAB is the Lennard-Jones parameter in nm
PM AB AB D
0.5 2
ΩD is a dimensionless function of T & energy of molecular interaction
Wilke-Lee modification Equation Chapman Enskog Model
4
(3.03  0.98 / M )10 T
0.5 3/2 1.43 102 T 1.75
DAB  AB DAB 
 AB D
0.5 2
PM AB   
1/3
 
1/3

PM AB        
0.5

 v  A  v  B    atomic diffusion volume

v
Prediction of Binary Diffusivities
Diffusivity of Liquids
 Semi-theoretical correlations using hydrodynamic theory

Stoke’s Einstein Equation Wilke-Chang Equation

T 1.173 1016 B M B  T
1/2
DAB  DAB 
6 B rA  B A0.6
rA is the radius of the solute molecule vA is the molal volume of the solute at normal BP
ϕB is an associate parameter for solvent B

Hayduk and Minhas Equation

1.0973 1015 T 1.29  PB0.5 / PA0.42 
DAB 
 B0.92 B0.23
P  v 1/4

P is the parachor
Diffusivity in Solids
 Mechanism of diffusion in solids is very complex

 Factors affecting diffusion in solids

 Diffusing atom, molecule or ion
 Nature of the solid structure (porous or non-porous, crystalline or amorphous)
 Type of solid material (metallic, ceramic, polymeric, biological, etc.)

Porous Solids
 Membrane separation, leaching, adsorption and drying
 Three types of diffusion mechanism occurs
Case 1: Mean free path for diffusion is small compared to pore diameter
d/λ > 20
 Molecule-molecule collisions predominate
 Molecule-wall collisions are minimal
 Ordinary Diffusion Mechanism holds good under this situation
 Apply Fick’s law of diffusion NA
y
NA  CDAB NA
ln
 N A  NB  A2

Z N A  NB NA
 y A1
 N A  NB 
Porous Solids
Case 2: Mean free path for diffusion is large compared to pore diameter
d/λ < 0.2
 Molecule-wall collisions predominate
 Molecule-molecule collisions are minimal
 Knudsen Diffusion Mechanism holds good under this situation
 Apply Knudsen diffusion equation
DK , A
NA   p A1  p A2 
RTl
Case 3: 0.2 < d/λ < 20
 Molecule-wall collisions and Molecule-molecule collisions happens
 Both Molecular Diffusion and Knudsen Diffusion Mechanism holds good under this
situation
NA  DAB 
1    y A2
NA 
CDAB NA
ln
 N A  NB   DKA 
Z N A  NB NA  DAB 
  y A1
 N A  N B   DKA 
1
Polymers
Thin, dense, nonporous polymer membranes are widely used to separate
gas and liquid mixtures
 Pressure gradient is the driving force
 Diffusion takes place from high pressure region to low pressure region
 For Gaseous species PMA is the permeability of the species
NA  PMA  p A1  p A2  PMA  DA H A
Z DA is the diffusivity, H A is the Henry's law constant

PMA is the permeability of the species

 For Liquid species
NA  PMA
 C A1  C A2  PMA  DA K A
Z DA is the diffusivity, K A is the partition coefficient

Cellular Solids
 Wood, cork, sponge, foams, etc.
 Drying, treatment with preservatives, fire retardants and other chemicals
 Movement of molecules takes place by capillary, pressure permeability and diffusion
 Crystalline Solids

Interstitial Mechanism
 Crystalline Solids

Vacancy Mechanism
 Crystalline Solids

Interstitialcy Mechanism
 Unsteady State Diffusion
z
Δy
Δx
(x+Δx, y+Δy, z+Δz)

NA(x) (x, y, z) NA(x+Δx)

Δz

x
y

Conservation of mass Rate of input of A – Rate of output of A = Rate of accumulation of A

C A
N A x yz  N A x x yz   xyz 
t
 Unsteady State Diffusion
C A
 N A x  N A xx  yz   xyz  t
N A x x  NA x  C
 A
N A

C A
Applying Fick’s Law
x t x t

C A  2C A
 DAB 2 Fick’s second Law of Diffusion
t x

C A   2C A  2C A  2C A 
 DAB  2  2  2  For Three dimensional case
t  x y z 
Interface Mass Transfer
 Example: Turbulent flow of water through a circular pipe in which the inside of the
pipe is coated with fused salt
 Inside cross section of the pipe, three layer exists
 Laminar, Laminar sub-layer, Turbulent
 Molecular Diffusion and Eddy Diffusion
Mass Transfer Coefficient

k mass flux k A
N  C CA
N
concentration difference C A Ai Ab

k - one component diffusing other stagnant

k' - equimolar counter diffusion
kc / k’c - molar concentration difference kL / k’L - molar concentration difference
ky / k’y - mole fraction difference kx / k’x - mole fraction difference
kG / k’G - partial pressure difference
Mass Transfer Coefficients

One component
Equimolar Counter
Driving Force Coefficient diffusing other Units of Coefficient
Diffusion
stagnant

Mole Fraction Difference ky / k’y NA = k’y ΔyA NA = ky ΔyA Kmol/m2s mole fraction

Partial Pressure Difference kG / k’G NA = k’G ΔpA NA = kG ΔpA Kmol/m2s Pa

Molar Concentration
kc / k’c NA = k’c ΔCA NA = kc ΔCA m/s
Difference

Mole Fraction Difference kx / k’x NA = k’x ΔxA NA = kx ΔxA Kmol/m2s mole fraction

Molar Concentration
kL / k’L NA = k’L ΔCA NA = kL ΔCA m/s
Difference
 Relationship among Mass Transfer Coefficients
yAi - mole fraction of A in the fluid-solid interface
yAb - mole fraction of A in the bulk of the fluid
CAi , CAb , pAi , pAb
N A  k y  y Ai  y Ab 


N A  kc C Ai  C Ab   kcC y Ai  y Ab 

N A  kG  pAi  pAb   kG P y Ai  y Ab 

k y  kcC  k G P ky'  kc' C  kG' P

k x  kL C kx'  kL' C
Theories of Mass Transfer
Film Theory
Solute concentration decreases as distance from the wall increases

Most of the mass transfer occurs by molecular diffusion –

Diffusional Sub-layer

Eddy diffusion occurs in the Turbulent core

Molecular diffusion & Eddy diffusion occurs in the Buffer zone

Proposed by Nernst (1904)

Entire concentration change is confined with an effective film of
thickness Z

N A  kC  C Ai  C Ab   CAi  CAb 
DAB
Z
 Theories of Mass Transfer
Penetration Theory

Proposed by Higbie (1935)

Eddies move from the bulk of the fluid stream to the interface at definite intervals
(they stay at the interface for a short but fixed period of time)

NA  2
DAB

CAi  CAb 
 Theories of Mass Transfer
Film Penetration Theory
Proposed by Toor and Marchello (1958)
Combines both Film and Penetration theory

Surface Renewal Theory

Proposed by Danckwerts
Eddies move from the bulk of the fluid stream to the interface at definite intervals
(they stay at the interface for a short but not for fixed period of time)
NA  DAB S CAi  CAb 
S  fraction rate of replacement of elements
 Theories of Mass Transfer
Surface Stretch Theory

Proposed by Lightfoot and his coworkers

Eddies move from the bulk of the fluid stream to the interface at definite intervals
(Mass Transfer at the interface varies with time periodically)

 DAB 
AA 
 r  r 
KL  
r 2
 A  d

0
 A
 r 
 Dimensional Analysis
 A powerful tool which simplifies experimental and empirical study of a process
 Multiple variables can be grouped into few dimensionless groups and analyzed
 Major limitation is that it need minimal experimental results
Dimensional Numbers in Mass Transfer
Schmidt Number
 Schmidt Number
 Lewis Number
 Sherwood Number Sc  momentum diffusivity Sc     D
mass diffusivity DAB AB

Sherwood Number
Lewis Number
k Sh  k L
'L
Sh  c Sh  k L
C C yB , M

Le    C kD
DAB DAB DAB
Le  thermal diffusivity
mass diffusivity DAB p AB
Stanton Number
 

 Pr
Sc
  DAB 
Le  k  
C p  DAB  C p  
 k 
St  Sh  kuc
D
 Re Sc
 Analogies Between Heat, Mass and Momentum Transfer
Conditions that should be satisfied for developing the analogy expressions:
 The physical properties are constant
 No energy or mass is produced within the system by means of chemical reaction
 Energy is neither absorbed nor emitted by the system
 The rate of mass transfer is low so that the velocity profile is not affected by mass transfer
 There is no viscous dissipation

Reynolds Analogy Chilton-Colburn Analogy

 Only turbulent core is present  Only turbulent core is present
 Velocity, Temp. & Concn. Profiles are matching  Velocity, Temp. & Concn. Profiles are matching
 All diffusivities are same  Diffusivities are not same

  DAB   N N
Pr Sc 1
f  h k
 Pr   c  Sc 
2/3 2/3

2 C p u u0
0
f  h  kc
2 C p  u u0
0
 Analogies Between Heat, Mass and Momentum Transfer

Taylor-Prandtl Analogy Von-Karman Analogy

 Turbulent core & laminar sublayer is present

 Diffusivities are not same  Turbulent core, laminar sublayer & buffer layers is
present
f f  Universal velocity profile equations are applicable
kc  h  2  2  Diffusivities are not same
u0 C p u   
f Sc 1  1  5 f Pr 1 
0 1  5
 2
   2
 
   

f f
kc  h  2  2
u0 C p u f   f  
0 1  5  Sc 1  ln  5Sc6 1   1  5  Pr 1  ln  5 Pr6 1  
2   2  
 Phase Equilibrium
Interphase Mass Transfer Two Immiscible Phases

Chemical Potentials of the constituents in all the phases should be

Equilibrium Identical
 Phase Equilibrium

 AG  y Ai 
y 
N A  k y  y AG  y Ai   kx  xAi  xAL      kx
   
 AL  xAi 
x  ky
 

Overall Mass Transfer Coefficient

N A  K y  y AG  y   K x  x  xAL 
* *

   
Equilibrium Distribution Diagram
General Concepts
 For a given temperature & pressure, there exists a set of equilibrium compositions
which is represented by a Distribution Diagram.
 For a system in equilibrium, there is no net diffusion of components between the
phases
 For a system not in equilibrium, diffusion will occur between the phases leading to a
state of equilibrium where the chemical potentials for any given component are
equal in all phases

Simple relationship equations

For liquid of ideal solution &

For very dilute solutions
gas behaves as a ideal gas

yx P S

P yxH
P
 Phase Equilibrium

N A  K y  y AG  y A*   K x  xA*  xAL 
   

Relationship between k and K

' 

y
 AG  y A
*  y
  AG

 y Ai
 y  y *
  Ai
 A  m  x
Ai
x AL 
    

N A  K y  y AG  y A*  N A  k y  y AG  y Ai   kx  xAi  xAL 

   

NA NA NA
Ky ky kx
 Relationship between k and K


 *   y   y  y * NA NA NA 1 1 1
y
 AG y A   AG
y Ai   Ai A   m '
 m '
 K y ky kx K y ky kx
 *   *  
x
 A  x  x
AL   A
 x  x
Ai   Ai
 x 
AL 
NA 1 NA NA
 
1 1 1
 '' 
1
 K x m k y kx
''
K x m k y kx
Gas Phase Controlled Liquid Phase Controlled
Systems Systems

Solute in the gas phase is Solute in the gas phase is

readily soluble in the liquid sparingly soluble in the liquid
m‘ will be very small m‘’ will be very large

1 1 1 1
 
K y ky K x kx